Organic electroluminescent device based on 2,5-diaminoterephthalic acid derivatives

ABSTRACT

The invention relates to an organic electroluminescent device which contains 2,5-diaminoterephthalic acid derivatives of formula 1a as emitter substances in one or several emitter layers in a pure or doped manner. The ring A is a triple unsaturated benzene ring wherein R 4′  and R 8′  are zero or ring A is a double unsaturated ring respectively provided with a double bond in the 1,2 position and 4,5 position, and wherein R 10  is a nitrile radical —CN or a radical C(═X 1 )—X 2 R 1 , R 11  is a nitrile radical —CN or a radical —C(═X 3 )—X 4 R 5 , X 1  and X 3  are oxygen, sulfur or imino, X 2  and X 4  are oxygen, sulfur or optionally substituted amino, R 1 –R 8 , R 4′  and R 8′  are H, C1–20-alkyl, aryl, heteroaryl, R 4  and R 8  can be halogen, nitro, cyanogen or amino, R 2 –R 4 , R 6 –R 8 , R 4′  and R 8′  can be trifluoromethyl or pentafluorophenyl, and wherein certain radicals can form a saturated or unsaturated ring. The devices are characterized by narrow emission bands, low driver voltages, high photometric efficiency and high thermal stability within a broad spectral range

CROSS REFERENCE TO RELATED APPLICATION

This application is a national stage of PCT/DE02/03110 filed Aug. 21, 2002, and based upon DE 101 41 266.5 filed Aug. 21, 2001 under the International Convention.

FIELD OF THE INVENTION

The present invention relates to a new organic electroluminescent device based on 2,5-diaminoterephthalic acid derivatives. Said derivatives are emitter substances for organic light-emitting diodes (OLED).

BACKGROUND TO THE INVENTION

Organic light-emitting diodes, which have long been known, use the electroluminescence of certain organic compounds. An OLED's structure and the tasks of its individual layers are exemplified in FIG. 1:

A layer sequence of organic substances is arranged between two electrodes, of which at least one must be translucent, each organic substance having a specific function within the device.

-   1. The cathode consists of a base metal or an alloy (e.g. aluminium     or calcium) and has the function of injecting electrons; -   2. The buffer layer consists of certain metal salts or the oxides     thereof, e.g. LiF, and has the function of improving the electron     injection into the layer 3; -   3. The electron conductor can e.g. consist of Alq3     (tris-(8-hydroxychinolinato)-aluminium) and conducts the electrons     from the cathode to the emitting layer or the hole conductor inside     the device; -   4. The hole conductor mainly consists of triphenylamine derivatives;     several hole conductor layers can be provided whose characteristics     are adapted to the device and whose function is to transport the     holes to the emitting layer; -   5. The anode consists of ITO which injects the holes into the hole     transport layer; -   6. The substrate consists of a transparent material, e.g. glass.

An arrangement of the type described above emits green light generated due to the excitation of Alq3 by the excitons formed from the holes and electrons.

However, such a simple arrangement has several drawbacks:

-   1. Alq3 only emits light in the green spectral range; -   2. The emission band of Alq3 is too broad.

Said drawbacks can in part be eliminated by doping. This means that one or more substances are co-evaporated during the diode's production process. In general, these substances are contained in the Alq3 layer in an amount ranging up to a few percent. Said co-evaporation process is difficult to control.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the layered structure of an organic light-emitting diode.

FIG. 2 shows an embodiment of the layered structure of an organic light-emitting diode of the present invention.

SUMMARY AND DETAILED DESCRIPTION OF THE INVENTION

The invention relates to new emitter substances which eliminate the known drawbacks of Alq3 both as an emitter substance and a host material for dopants. As a consequence, Alq3 is generally required as an electron conductor only. The new emitter substances are characterized by:

-   1. narrower emission bands; -   2. the devices cover a broad spectral range due to the fact that     different substances are used, either in layers separated from one     another or in mixed layers; -   3. low driver voltages; -   4. high photometric efficiency (low power consumption); -   5. high luminance (emission intensity); -   6. high thermal stability.

For the purposes of the invention, the term “device” relates to an arrangement in which the substrate and layers are arranged on top of one another according to FIG. 1 or 2, but which has not yet been incorporated into a light-emitting diode. Such an inventive device can in principle have the structure shown in FIG. 1 or 2. In said devices, the 2,5-diaminoterephthalic acid derivatives can be co-evaporated either alone or conjointly with other compounds, optionally even with known compounds, to obtain emitters. These emitters are used in combination with known hole conductors.

The object of the invention is to provide new organic electroluminescent devices using improved emitter substances.

According to the invention, the organic electroluminescent device contains 2,5-diaminoterephthalic acid derivatives of the following formula 1a in one or several emitter layers in a pure or doped form in a device

wherein the ring A is a triply unsaturated benzene ring wherein R^(4′) and R^(8′) are omitted, or the ring A is a doubly unsaturated ring having a double bond in the 1,2-position and in the 4,5-position, and

wherein R¹⁰ represents a nitrile radical —CN or a radical —C(═X¹)—X²R¹,

R¹¹ is a nitrile radical —CN or a radical —C(═X³)—X⁴R⁵,

wherein

X¹ and X³ can be the same or different atoms or groups, such as oxygen, sulphur, imino, preferably oxygen;

X² and X⁴ can be the same or different atoms or groups, such as oxygen, sulphur, amino, wherein the amino nitrogen can be substituted with alkyl having 1 to 20 C-atoms, preferably C1 to C8, or with aryl, e.g. phenyl, naphthyl, or with heteroaryl, e.g. cumaryl, pyridyl, chinolyl, indolyl, carbazolyl, imidazolyl, thienyl, thiazolyl, furyl, oxazolyl;

R¹ to R⁸, R^(4′) and R^(8′) can be the same or different substituents, such as hydrogen, alkyl having 1 to 20 atoms, preferably C1 to C8; aryl, e.g. phenyl, naphthyl, as well as heteroaryl, e.g. cumaryl, pyridyl, chinolyl, indolyl, carbazolyl, imidazolyl, thienyl, thiazolyl, furyl, oxazolyl, and the aforesaid radicals can be substituted singly or doubly with atoms or groups, e.g. di-C1–C3-amino or alkoxy with alkyl radicals C1 to C10, preferably C1–C4; C1–C4 alkyl, cyano, fluorine, chlorine, bromine or iodine as well as phenyl;

R⁴ and R⁸ can also be the same or different substituents, such as halogen, nitro, cyano or amino;

R² to R⁴, R⁶ to R⁸, R^(4′) and R^(8′) can also be trifluoromethyl or pentafluorophenyl,

and wherein the following radicals can form a saturated or unsaturated ring

X¹ and X², R¹ and R², R² and X², R² and R³, R³ and R⁴, R⁴ and X³, X³ and X⁴, R⁵ and X⁴, R⁶ and X⁴, R⁶ and R⁷, R⁷ and R⁸, R⁸ and X¹, R³ and R^(4′), R⁷ and R^(8 ′), R⁴ and R^(4′), and R⁸ and R^(8′), to which rings further rings can be fused.

It is preferred that R², R³, R⁶ and R⁷ be trifluoromethyl or pentafluorophenyl, R⁴ and R⁸ be halogen, nitro, cyano or amino, and the other substituents have the meaning indicated above.

It is particularly preferred that R⁴ and R⁸ be trifluoromethyl or pentafluorophenyl, and the other substituents have the meaning indicated above.

As regards spelling in the following text, R¹⁻⁸ means R¹ to R⁸; X^(2,4) means X² and X⁴; R^(4′,8′) means R^(4′) and R^(8′).

The invention also relates to new 2,5-diaminoterephthalic acid derivatives of the formula 19

wherein X¹ is O and X² is O or N; R² and R⁶ are methylene (—CH₂—) which can be substituted with trifluoromethyl, R³ and R⁷ are the same or different, H, C1–C8 alkyl, aryl or heteroaryl, and R⁴ and R⁸ are the same or different, H, alkyl, aryl or trifluoromethyl. It is particularly preferred that alkyl be C1–C4 alkyl, aryl be phenyl or naphthyl, and heteroaryl be pyridyl, thienyl or furyl.

In general, it is preferred that substituents arranged opposite one another, such as X¹ and X³, X² and X⁴, R¹ and R⁵, R² and R⁶, R³ and R⁷, R⁴ and R⁸, R^(4′) and R^(8′), and R¹⁰ and R¹¹, are the same, i.e. not different, in all structures according to the invention.

The electroluminescent devices according to the invention preferably contain 2 to 3 different substances which are mixed with one another in one device.

Now, preferred structures will be listed, wherein in the structures 1

-   X¹ and X² can be members of a ring provided X¹=N and there is no     substituent R¹ in case X²≠N;

-   X² and R¹ can be members of a ring provided X²=N;

-   X² and R² can be members of a ring provided X²=N;

-   R² and R³ can be members of a ring;

-   R³ and R⁴ can be members of a ring;

-   R⁴ and X³ can be members of a ring provided X³=N;

-   X³ and X⁴ can be members of a ring provided X³=N and there is no     substituent R¹ in case X⁴≠N;

-   X⁴ and R⁵ can be members of a ring provided X⁴=N;

-   X⁴ and R⁶ can be members of a ring provided X⁴=N;

-   R⁶ and R⁷ can be members of a ring;

R⁷ and R⁸ can be members of a ring;

-   R⁸ and X¹ can be members of a ring provided X¹=N;

wherein symmetric combinations of the aforesaid structural types are preferred

-   X¹ and X² as well as X³ and X⁴ can be members of a ring provided     X^(1,3)=N and there is no substituent R^(1,5) in case X^(2,4)≠N;

-   X² and R¹ can be members of a ring provided X^(2,4)=N;

-   X² and R² as well as X⁴ and R⁶ can be members of a ring provided     X^(2,4)=N;

-   R² and R³ as well as R⁶ and R⁷ can be members of a ring;

R³ and R⁴ as well as R⁷ and R⁸ can be members of a ring;

-   R⁴ and X³ as well as R⁸ and X¹ can be members of a ring provided     X^(1,3)=N;

and wherein in the structure 2

X¹ and X² can be members of a ring provided X¹=N and there is no substituent R¹ in case X²≠N;

X² and R¹ can be members of a ring provided X²=N;

X² and R² can be members of a ring provided X²=N;

-   R² and R³ can be members of a ring;

-   R³ and R⁴ can be members of a ring;

-   R⁴ and R^(4′) can be members of a ring;

-   R⁴ and X³ can be members of a ring provided X³=N;

-   X³ and X⁴ can be members of a ring provided X³=N and there is no     substituent R⁵ in case X⁴≠N;

X⁴ and R⁵ can be members of a ring provided X⁴=N;

-   X⁴ and R⁶ can be members of a ring provided X⁴=N;

-   R⁶ and R⁷ can be members of a ring;

-   R⁷ and R⁸ can be members of a ring;

-   R⁸ and R^(8′) can be members of a ring;

-   R⁸ and X¹ can be members of a ring provided X¹=N;

wherein symmetric combinations of the aforesaid structural types are preferred

-   X¹ and R² as well as X³ and X⁴ can be members of a ring provided     X^(1,3)=N and there is no substituent R^(1,5) in case X^(2,4)≠N;

-   X² and R¹ can be members of a ring provided X^(2,4)=N;

-   X² and R² as well as X⁴ and R⁶ can be members of a ring provided     there is no substituent R^(1,5) in case X^(2,4)≠N;

-   R² and R³ as well as R⁶ and R⁷ can be members of a ring;

-   R³ and R^(4′) as well as R⁷ and R^(8′) can be members of a ring;

-   R⁴ and R^(4′) as well as R⁸ and R^(8′) can be members of a ring;

-   R⁴ and X³ as well as R⁸ and X¹ can be members of a ring provided     X^(1,3)=N;

and wherein in the structures 3

-   R² and R³ can be members of a ring;

-   R³ and R⁴ can be members of a ring;

-   R⁶ and R⁷ can be members of a ring;

-   R⁷ and R⁸ can be members of a ring;

-   R² and R³ as well as R⁶ and R⁷ can be members of a ring;

-   R³ and R⁴ as well as R⁷ and R⁸ can be members of a ring;

and wherein in the structures 4

-   R² and R³ can be members of a ring;

-   R³ and R^(4′) can be members of a ring;

-   R⁴ and R^(4′) can be members of a ring;

-   R⁶ and R⁷ can be members of a ring;

-   R⁷ and R^(8′) can be members of a ring;

-   R⁸ and R^(8′) can be members of a ring;

-   R² and R³ as well as R⁶ and R⁷ can be members of a ring;

-   R³ and R^(4′) as well as R⁷ and R^(8′) can be members of a ring;

-   R⁴ and R^(4′) as well as R⁸ and R^(8′) can be members of a ring;

The emitter substances of formula 1, i.e. derivatives of 2,5-diaminoterephthalic acid, can be obtained by reacting esters of cyclohexane-2,5-dione-1,4-dicarboxylic acid with primary anilines or amines, subsequent oxidation and, optionally, further modification. Said derivatives can be processed into cyclized derivatives in a manner known per se, as shown e.g. in Formula Diagrams I and II.

The compounds of formula 3 can be produced by reacting the respective 2,5-diaminoterephthalic acid amides with dehydrating agents.

In order to produce the compounds of formula 4, wherein R⁴ and R⁸ as well as R^(4′) and R^(8′) are not H, the esters of 2,5-diaminocyclohexane-1,4-dicarboxylic acid are converted into hydrazides and reacted with potassium hexacyanoferrate(III) in order to obtain aldehydes. These 2,5-diaminocyclohexane-1,4-dicarbaldehydes can be converted into oximes which are reacted with formic acid in order to obtain the compounds of formula 4.

Examples of the new emitters according to formula 1 are listed in Table 1:

TABLE 1 2,5-diaminoterephthalic acid derivatives Substance X¹ X² R³ R¹

1.0

1.1 O O

—CH₃

1.2 O O

—CH₃

1.3 O O

—CH₃

1.4 O O

—CH₃

1.5 O O

—C₂H₅

1.6 O O

—CH₃

1.7 O O

—CH₃

1.8 O O

—CH₃

1.9 O O

—CH₃

1.10 O O

—CH₃

1.11 O O

—CH₃

1.12 O O

—CH₃

1.13 O O

—CH₃

1.14 O O

—CH₃

1.15 O O

—CH₃

1.16 O O

—CH₃

1.17 O O

—CH₃

1.18 O O

—CH₃

1.19 O O

—CH₃

1.20 O O

—CH₃

1.21 O O

—CH₃

1.22 O O

—CH₃

1.23 O O

—CH₃

1.24 O O

—CH₃

1.25 O O —C₄H₉ —CH₃

1.26 O O

—CH₃

1.27 O O

—CH₃

1.28 O O

—CH₃

1.29 O O

—CH₃

1.30 O O

—CH₃

1.31 O O

—CH₃

1.32 O O

—CH₃

1.33 O O

—CH₃

1.34 O O

—CH₃

1.35 O O

—CH₃

1.36 O O

—CH₃

1.37 O O

—CH₃

1.38 O O

—CH₃

1.39 O O

—CH₃

1.40 O O

—CH₃

1.41 O O

—CH₃

1.42 O O

—CH₃

1.43 O O

—CH₃ 1.44 O O

—CH₃ 1.45 O O

—CH₃ 1.46 O O

—CH₃ 1.47 O O

—CH₃ 1.48 O O

—CH₃ 1.49 O O

—CH₃ 1.50 O O

—CH₃ 1.51 O O

—CH₃ 1.52 O O

—CH₃ 1.53 O O

—CH₃ 1.54 O O

—CH₃ 1.55 O O —CH₃ 1.56 O O

—CH₃ 1.57 O O

—CH₃ 1.58 O O

—CH₃ 1.59 O O

—CH₃ 1.60 O O

—CH₃ 1.61 O O

—CH₃ 1.62 O O

—CH₃ 1.63 O O

—CH₃ 1.64 O O

—CH₃ 1.65 O O

—CH₃ 1.67 O O

—CH₃ 1.68 O O

—CH₃ 1.69 O O

—CH₃ 1.70

—CH₃ 1.71 O N

1.72 O N

1.73 O O

—CH₃ 1.74 O O

—CH₃ 1.75 O O

—CH₃

17.0 17.1

—CH₃ 17.2

—CH₃ 17.3

— 17.4

—

5.0 5.1

11.0 11.1 O O

—CH₃ Substance R² R⁴ X⁴ X³

1.0

1.1 H H O O

1.2 —CH₃ H O O

1.3 H H O O

1.4 H H O O

1.5 H H O O

1.6 H H O O

1.7 H H O O

1.8 H H O O

1.9 H H O O

1.10 H H O O

1.11 H H O O

1.12 H H O O

1.13 H H O O

1.14 H H O O

1.15 H H O O

1.16 H H O O

1.17 H H O O

1.18 H H O O

1.19 —CH₃ H O O

1.20 H H O O

1.21 H H O O

1.22 H H O O

1.23 H H O O

1.24 H H O O

1.25 H H O O

1.26 H H O O

1.27 H H O O

1.28 H H O O

1.29 —CH₃ H O O

1.30 H H O O

1.31 —CH₃ H O O

1.32 —CH₃ H O O

1.33 —CH₃ H O O

1.34

H O O

1.35 H H O O

1.36 —CH₃ H O O

1.37 H H O O

1.38

H O O

1.39

H O O

1.40

H O O

1.41

H O O

1.42

H O O

1.43 H H O O 1.44 —CH₃ H O O 1.45 —CH₃ H O O 1.46 —CH₃ H O O 1.47 —CH₃ H O O 1.48 —CH₃ H O O 1.49 —CH₃ H O O 1.50 —CF₃ H O O 1.51 —CF₃ H O O 1.52 —CF₃ H O O 1.53 —CF₃ H O O 1.54 —CF₃ H O O 1.55 —CF₃ H O O 1.56

H O O 1.57

H O O 1.58

H O O 1.59

H O O 1.60

H O O 1.61

H O O 1.62

H O O 1.63

H O O 1.64

H O O 1.65 —CH₃ H O O 1.67

H O O 1.68

H O O 1.69

H O O 1.70

H O O 1.71 H H N O 1.72

H N O 1.73 —CH₃

O O 1.74

O O 1.75

O O

17.0 17.1 —CH₃ H

17.2 —CH₃ H

17.3 —CH₃ H

17.4 —CH₃ H

5.0 5.1 —CH₃ H O O

11.0 11.1 —CH₃ H

Substance R⁸ R⁵ R⁶

1.0

1.1 H —CH₃ H

1.2 H —CH₃ —CH₃

1.3 H —CH₃ H

1.4 H —CH₃ H

1.5 H —C₂H₅ H

1.6 H —CH₃ H

1.7 H —CH₃ H

1.8 H —CH₃ H

1.9 H —CH₃ H

1.10 H —CH₃ H

1.11 H —CH₃ H

1.12 H —CH₃ H

1.13 H —CH₃ H

1.14 H —CH₃ H

1.15 H —CH₃ H

1.16 H —CH₃ H

1.17 H —CH₃ H

1.18 H —CH₃ H

1.19 H —CH₃ —CH₃

1.20 H —CH₃ H

1.21 H —CH₃ H

1.22 H —CH₃ H

1.23 H —CH₃ H

1.24 H —CH₃ H

1.25 H —CH₃ H

1.26 H —CH₃ H

1.27 H —CH₃ H

1.28 H —CH₃ H

1.29 H —CH₃ —CH₃

1.30 H —CH₃ H

1.31 H —CH₃ —CH₃

1.32 H —CH₃ —CH₃

1.33 H —CH₃ —CH₃

1.34 H —CH₃

1.35 H —CH₃ H

1.36 H —CH₃ —CH₃

1.37 H —CH₃ H

1.38 H —CH₃

1.39 H —CH₃

1.40 H —CH₃

1.41 H —CH₃

1.42 H —CH₃

1.43 H —CH₃ H 1.44 H —CH₃ —CH₃ 1.45 H —CH₃ —CH₃ 1.46 H —CH₃ —CH₃ 1.47 H —CH₃ —CH₃ 1.48 H —CH₃ —CH₃ 1.49 H —CH₃ —CH₃ 1.50 H —CH₃ —CF₃ 1.51 H —CH₃ —CF₃ 1.52 H —CH₃ —CF₃ 1.53 H —CH₃ —CF₃ 1.54 H —CH₃ —CF₃ 1.55 H —CH₃ —CF₃ 1.56 H —CH₃

1.57 H —CH₃

1.58 H —CH₃

1.59 H —CH₃

1.60 H —CH₃

1.61 H —CH₃

1.62 H —CH₃

1.63 H —CH₃

1.64 H —CH₃

1.65 H —CH₃ —CH₃ 1.67 H —CH₃

1.68 H —CH₃

1.69 H —CH₃

1.70 H —CH₃

1.71 H

H 1.72 H

1.73

—CH₃ —CH₃ 1.74

—CH₃

1.75

—CH₃

17.0 17.1 H —CH₃ —CH₃ 17.2 H —CH₃ —CH₃ 17.3 H — —CH₃ 17.4 H — —CH₃

5.0 5.1 H —CH₃ —CH₃

11.0 11.1

—CH₃ —CH₃ Substance R⁷

1.0

1.1

1.2

1.3

1.4

1.5

1.6

1.7

1.8

1.9

1.10

1.11

1.12

1.13

1.14

1.15

1.16

1.17

1.18

1.19

1.20

1.21

1.22

1.23

1.24

1.25 —C₄H₉

1.26

1.27

1.28

1.29

1.30

1.31

1.32

1.33

1.34

1.35

1.36

1.37

1.38

1.39

1.40

1.41

1.42

1.43

1.44

1.45

1.46

1.47

1.48

1.49

1.50

1.51

1.52

1.53

1.54

1.55 1.56

1.57

1.58

1.59

1.60

1.61

1.62

1.63

1.64

1.65

1.67

1.68

1.69

1.70

1.71

1.72

1.73

1.74

1.75

17.0 17.1

17.2

17.3

17.4

5.0 5.1

11.0 11.1

Substance X¹ X² R³

19.0

19.1 O O

19.2 O O

19.3 O O

19.4 O O

19.5 O O

19.6 O O

19.7 O O

19.8 O O

19.9 O O

19.10 O O

19.11 O O

19.12 O O

19.13 O O

19.14 O O

19.15 O O

19.16 O O

19.17 O O

7.0 7.1 O O

7.2 O O

13.0 13.1 O O

13.2 O O

Substance R² R¹ R⁴ X⁴ X³ R⁸

19.0

19.1 —CH₂— — H O O H

19.2 —CH₂— — H O O H

19.3 —CH₂— — H O O H

19.4 —CH₂— — H O O H

19.5 —CH₂— — H O O H

19.6 —CH₂— — H O O H

19.7 —CH₂— — H O O H

19.8 —CH₂— — H O O H

19.9 —CH₂— — H O O H

19.10 —CH₂— — H O O H

19.11 —CH₂— — H O O H

19.12 —CH₂— — H O O H 19.13 —CH₂— — H O O H 19.14 —CH₂— — H O O H 19.15 —CF₂— — H O O H 19.16

— H O O H 19.17

— H O O H

7.0 7.1 —CH₂— H O O H 7.2 —CH₂— H N O H

13.0 13.1

—CH₃ H N O H 13.2

—CH₃ H N O H Substance R⁶ R⁵ R⁷

19.0

19.1 —CH₂— —

19.2 —CH₂— —

19.3 —CH₂— —

19.4 —CH₂— —

19.5 —CH₂— —

19.6 —CH₂— —

19.7 —CH₂— —

19.8 —CH₂— —

19.9 —CH₂— —

19.10 —CH₂— —

19.11 —CH₂— —

19.12 —CH₂— —

19.13 —CH₂— —

19.14 —CH₂— —

19.15 —CF₂— —

19.16

—

19.17

—

7.0 7.1 —CH₃ —CH₃

7.2

—CH₃

13.0 13.1 —CH₂—

13.2 —CH₂—

Substance X¹ R¹ X² R² R³ R⁴ R⁵ X³ X⁴ R⁶ R⁷

20.0 20.1 O —CH₃ O

H —CH₃ O O

20.2 O —CH₃ O

H —CH₃ O O

20.3 O —CH₃ O

H —CH₃ O O

20.4 O —CH₃ O

H —CH₃ O O

8.0 8.1 O —CH₃ O

H —CH₃ O O —CH₃

8.2 O —CH₃ O

H —CH₃ O O

8.3 O —CH₃ O

—CH₃ O O

Substance R⁸

20.0 20.1 H 20.2 H 20.3 H 20.4 H

8.0 8.1 H 8.2 H 8.3 H Substance X¹ X² R³ R² R¹ R⁴ X⁴ X³ R⁸ R⁶ R⁵ R⁷

14.0 14.1 O —CH₃ O —CH₃

—CH₃ O O

H 14.2 O —CH₃ O

—CH₃ O O

H Substance R¹ X² X¹ R⁴ R³ R² R⁵ X⁴ X³

18.0 18.1

O H

—CH₃

O 18.2

O H

—CH₃

O 18.3

O H

—CH₃

O 18.4

O H

—CH₃

O

6.0 6.1

O H

—CH₃ —CH₃ O O 6.2

O H

—CH₃ O O

12.0 12.1 —CH₃ O O H

—CH₃

O 12.2 —CH₃ O O H

O

21.0 21.1 —CH₃ O O

—CH₃ O O

9.0 9.1 —CH₃ O O

—CH₃ O O 9.2 —CH₃ O O

O

15.0 15.1

O H

—CH₃ O O Substance R⁸ R⁷ R⁶

18.0 18.1 H

—CH₃ 18.2 H

—CH₃ 18.3 H

—CH₃ 18.4 H

—CH₃

6.0 6.1 H

—CH₃ 6.2 H

12.0 12.1 H

H 12.2 H

—CH₃

21.0 21.1

9.0 9.1 H

9.2 H

15.0 15.1

Substance X² R² R³ R⁴ X³ R⁵ R⁶ X⁴ R⁷

22.0 22.1 O —CH₃

—CH₃ —CH₃ O

10.0 10.1 O —CH₃

—CH₃ —CH₃ O

10.2 O

—CH₃ —CH₃ O

16.0 16.1 O

H O —CH₃ —CH₃ O

Substance R⁸ X¹ R¹

22.0 22.1

—CH₃

10.0 10.1 H O —CH₃ 10.2 H O —CH₃

16.0 16.1

—CH₃

TABLE 2 2,5-diamino-3,6-dihydroterephthalic acid derivatives Substance X¹ X² R³ R¹ R²

2.0

2.1 O O

—CH₃ H

2.2 O O

—CH₃ —CH₃

2.3 O O

—CH₃ H

2.4 O O

—CH₃ H

2.5 O O

—C₂H₅ H

2.6 O O

—CH₃ H

2.7 O O

—CH₃ H

2.8 O O

—CH₃ H

2.9 O O

—CH₃ H

2.10 O O

—CH₃ H

2.11 O O

—CH₃ H

2.12 O O

—CH₃ H

2.13 O O

—CH₃ H

2.14 O O

—CH₃ H

2.15 O O

—CH₃ H

2.16 O O

—CH₃ H

2.17 O O

—CH₃ H

2.18 O O

—CH₃ H

2.19 O O

—CH₃ —CH₃

2.20 O O

—CH₃ H

2.21 O O

—CH₃ H

2.22 O O

—CH₃ H

2.24 O O

—CH₃ H

2.25 O O —C₄H₉ —CH₃ H

2.26 O O

—CH₃ H

2.27 O O

—CH₃ H

2.28 O O

—CH₃ H

2.29 O O

—CH₃ —CH₃

2.30 O O

—CH₃ H

2.31 O O

—CH₃ —CH₃

2.32 O O

—CH₃ —CH₃

2.33 O O

—CH₃ —CH₃

2.34 O O

—CH₃

2.35 O O

—CH₃ H

2.36 O O

—CH₃ —CH₃

2.37 O O

—CH₃ H

2.38 O O

—CH₃

2.39 O O

—CH₃

2.40 O O

—CH₃

2.41 O O

—CH₃

2.42 O O

—CH₃

2.43 O O

—CH₃ H 2.44 O O

—CH₃ —CH₃ 2.45 O O

—CH₃ —CH₃ 2.46 O O

—CH₃

2.47 O O

—CH₃

2.48 O O

—CH₃ —CH₃ 2.49 O O

—CH₃ —CH₃ 2.50 O O

—CH₃ —CH₃ 2.51 O O

—CH₃ —CH₃ 2.52 O O

—CH₃ —CH₃ 2.53 O O

—CH₃ —CH₃ 2.54 O O

—CH₃ —CF₃ 2.55 O O

—CH₃ —CF₃ 2.56 O O

—CH₃ —CF₃ 2.57 O O

—CH₃ —CF₃ 2.58 O O

—CH₃ —CF₃ 2.59 O O

—CH₃ —CF₃ 2.60 O O

—CH₃

2.61 O O

—CH₃

2.62 O O

—CH₃

2.63 O O

—CH₃

2.64 O O

—CH₃

2.65 O O

—CH₃

2.66 O O

—CH₃

2.67 O O

—CH₃

2.68 O O

—CH₃

2.69 O O

—CH₃ —CH₃ 2.70 O O

—CH₃

2.71 O O

—CH₃

2.72 O O

—CH₃

2.73

—CH₃

2.74 O N

H 2.75 O N

2.76 O O

—CH₃ —CH₃ 2.78 O O

—CH₃

2.79 O O

—CH₃

Substance R^(4′) R^(4′) X⁴ X³ R⁸ R^(8′) R⁵

2.0

2.1 H H O O H H —CH₃

2.2 H H O O H H —CH₃

2.3 H H O O H H —CH₃

2.4 H H O O H H —CH₃

2.5 H H O O H H —CH₃

2.6 H H O O H H —CH₃

2.7 H H O O H H —CH₃

2.8 H H O O H H —CH₃

2.9 H H O O H H —CH₃

2.10 H H O O H H —CH₃

2.11 H H O O H H —CH₃

2.12 H H O O H H —CH₃

2.13 H H O O H H —CH₃

2.14 H H O O H H —CH₃

2.15 H H O O H H —CH₃

2.16 H H O O H H —CH₃

2.17 H H O O H H —CH₃

2.18 H H O O H H —CH₃

2.19 H H O O H H —CH₃

2.20 H H O O H H —CH₃

2.21 H H O O H H —CH₃

2.22 H H O O H H —CH₃

2.24 H H O O H H —CH₃

2.25 H H O O H H —CH₃

2.26 H H O O H H —CH₃

2.27 H H O O H H —CH₃

2.28 H H O O H H —CH₃

2.29 H H O O H H —CH₃

2.30 H H O O H H —CH₃

2.31 H H O O H H —CH₃

2.32 H H O O H H —CH₃

2.33 H H O O H H —CH₃

2.34 H H O O H H —CH₃

2.35 H H O O H H —CH₃

2.36 H H O O H H —CH₃

2.37 H H O O H H —CH₃

2.38 H H O O H H —CH₃

2.39 H H O O H H —CH₃

2.40 H H O O H H —CH₃

2.41 H H O O H H —CH₃

2.42 H H O O H H —CH₃

2.43 H H O O H H —CH₃ 2.44 F F O O F F —CH₃ 2.45 F F O O F F —CH₃ 2.46 F F O O F F —CH₃ 2.47 F F O O F F —CH₃ 2.48 H H O O H H —CH₃ 2.49 H H O O H H —CH₃ 2.50 H H O O H H —CH₃ 2.51 H H O O H H —CH₃ 2.52 H H O O H H —CH₃ 2.53 H H O O H H —CH₃ 2.54 H H O O H H —CH₃ 2.55 H H O O H H —CH₃ 2.56 H H O O H H —CH₃ 2.57 H H O O H H —CH₃ 2.58 H H O O H H —CH₃ 2.59 H H O O H H —CH₃ 2.60 H H O O H H —CH₃ 2.61 H H O O H H —CH₃ 2.62 H H O O H H —CH₃ 2.63 H H O O H H —CH₃ 2.64 H H O O H H —CH₃ 2.65 H H O O H H —CH₃ 2.66 H H O O H H —CH₃ 2.67 H H O O H H —CH₃ 2.68 H H O O H H —CH₃ 2.69 H H O O H H —CH₃ 2.70 H H O O H H —CH₃ 2.71 H H O O H H —CH₃ 2.72 H H O O H H —CH₃ 2.73 H H O O H H —CH₃ 2.74 H H N O H H

2.75 H H N O H H

2.76

O O

—CH₃ 2.78

O O

—CH₃ 2.79

O O

—CH₃ Substance R⁶ R⁷

2.0

2.1 H

2.2 —CH₃

2.3 H

2.4 H

2.5 H

2.6 H

2.7 H

2.8 H

2.9 H

2.10 H

2.11 H

2.12 H

2.13 H

2.14 H

2.15 H

2.16 H

2.17 H

2.18 H

2.19 —CH₃

2.20 H

2.21 H

2.22 H

2.24 H

2.25 H —C₄H₉

2.26 H

2.27 H

2.28 H

2.29 —CH₃

2.30 H

2.31 —CH₃

2.32 —CH₃

2.33 —CH₃

2.34

2.35 H

2.36 —CH₃

2.37 H

2.38

2.39

2.40

2.41

2.42

2.43 H

2.44 —CH₃

2.45 —CH₃

2.46

2.47

2.48 —CH₃

2.49 —CH₃

2.50 —CH₃

2.51 —CH₃

2.52 —CH₃

2.53 —CH₃

2.54 —CF₃

2.55 —CF₃

2.56 —CF₃

2.57 —CF₃

2.58 —CF₃

2.59 —CF₃

2.60

2.61

2.62

2.63

2.64

2.65

2.66

2.67

2.68

2.69 —CH₃

2.70

2.71

2.72

2.73

2.74 H

2.75

2.76 —CH₃

2.78

2.79

Substance X¹ X² R³ R¹ R² R⁴

37.0 37.1

—CH₃ —CH₃ H 37.2

—CH₃ H 37.3

— —CH₃ H 37.4

— —CH₃ H

23.0 23.1

—CH₃ H

30.0 30.1 O O

—CH₃ —CH₃ H Substance X⁴ X³ R⁸ R⁵ R⁶ R⁷ R^(4′) R^(8′)

37.0 37.1

H —CH₃ —CH₃

H H 37.2

H

—CH₃

H H 37.3

H — —CH₃

H H 37.4

H — —CH₃

H H

23.0 23.1 O O H —CH₃ —CH₃

H H

30.0 30.1

—CH₃ —CH₃

H

Substance X¹ X² R³ R² R¹ R⁴ X⁴ X³

39.0

39.1 O O

—CH₂— — H O O

39.2 O O

—CH₂— — H O O

39.3 O O

—CH₂— — H O O

39.4 O O

—CH₂— — H O O

39.5 O O

—CH₂— — H O O

39.6 O O

—CH₂— — H O O

39.7 O O

—CH₂— — H O O

39.8 O O

—CH₂— — H O O

39.9 O O

—CH₂— — H O O

39.10 O O

—CH₂— — H O O

39.11 O O

—CH₂— — H O O

39.12 O O

—CH₃— — H O O 39.13 O O

—CH₂— — H O O 39.14 O O

—CH₂— — H O O 39.15 O O

—CF₂— — H O O 39.16 O O

— H O O 39.17 O O

— H O O 39.18 O O

—CH₂— — H O O 39.19 O O

—CH₂— — H O O 39.20 O O

—CF₂— — H O O 39.21 O O

— H O O 39.22 O O

— H O O

25.0 25.1 O O

—CH₂— H O O 25.2 O O

—CH₂— H N O

32.0 32.1 O O

—CH₃ H N O 32.2 O O

—CH₃ H N O Substance R⁸ R⁶ R⁵ R⁷ R^(4′) R^(8′)

39.0

39.1 H —CH₂— —

H H

39.2 H —CH₂— —

H H

39.3 H —CH₂— —

H H

39.4 H —CH₂— —

H H

39.5 H —CH₂— —

H H

39.6 H —CH₂— —

H H

39.7 H —CH₂— —

H H

39.8 H —CH₂— —

H H

39.9 H —CH₂— —

H H

39.10 H —CH₂— —

H H

39.11 H —CH₂— —

H H

39.12 H —CH₂— —

H H 39.13 H —CH₂— —

H H 39.14 H —CH₂— —

H H 39.15 H —CF₂— —

H H 39.16 H

—

H H 39.17 H

—

H H 39.18 H —CH₂— —

H H 39.19 H —CH₂— —

H H 39.20 H —CF₂— —

H H 39.21 H

—

H H 39.22 H

—

H H

25.0 25.1 H —CH₃ —CH₃

H H 25.2 H

—CH₃

H H

32.0 32.1 H —CH₂—

H H 32.2 H —CH₂—

H H Substance X¹ R¹ X² R² R³ R⁴ R⁵ X³ X⁴ R⁶ R⁷ R⁸

40.0 40.1 O —CH₃ O

H —CH₃ O O

H 40.2 O —CH₃ O

H —CH₃ O O

H 40.3 O —CH₃ O

H —CH₃ O O

H 40.4 O —CH₃ O

H —CH₃ O O

H

26.0 26.1 O —CH₃ O

H —CH₃ O O —CH₃

H 26.2 O —CH₃ O

H —CH₃ O O

H 26.3 O —CH₃ O

—CH₃ O O

H Substance R^(4′) R^(8′)

40.0 40.1 H H 40.2 H H 40.3 H H 40.4 H H

26.0 26.1 H H 26.2 H H 26.3

H Substance X¹ R¹ X² R⁴ R² R³ R⁵ X³ X⁴ R⁶ R⁷ R⁸ R^(4′) R^(8′)

33.0 33.1 O —CH₃ O —CH₃

—CH₃ O O

H —CH₃ H 33.2 O —CH₃ O

—CH₃ O O

H

H Substance R¹ X² X¹ R⁴ R³ R² R⁵ X⁴ X³ R⁸ R⁷ R⁶ R^(4′) R^(8′)

38.0 38.1

O H

—CH₃

O H

—CH₃ H H 38.2

O H

—CH₃

O H

—CH₃ H H 38.3

O H

—CH₃

O H

—CH₃ H H 38.4

O H

—CH₃

O H

—CH₃ H H

24.0 24.1

O H

—CH₃ —CH₃ O O H

—CH₃ H H 24.2

O H

—CH₃ O O H

H H

31.0 31.1 —CH₃ O O H

—CH₃

O H

H H H 31.2 —CH₃ O O H

O H

—CH₃ H H Substance R¹ X² X¹ R^(4′) R³ R² R⁵ X⁴ X³ R^(8′) R⁷ R⁶ R⁴ R⁸

41.0 41.1 —CH₃ O O

—CH₃ O O

H H

27.0 27.1 —CH₃ O O

—CH₃ O O H

H H 27.2 —CH₃ O O

O H

H H Substance R¹ X² X¹ R⁴ R³ R² R⁵ X⁴ X³ R⁵ R⁷ R^(8′) R^(4′) R⁸

34.0 34.1

O H

—CH₃ —CH₃ O O

H H Substance X² R² R³ R⁴ X³ R⁵ R⁶ X⁴ R⁷ R⁸ X¹ R¹

43.0 43.1 O —CH₃

—CH₃ —CH₃ O

—CH₃

29.0 29.1 O —CH₃

—CH₃ —CH₃ O

H O —CH₃ 29.2 O

—CH₃ —CH₃ O H O —CH₃

36.0 36.1 O

H O —CH₃ —CH₃ O

—CH₃ Substance R^(4′) R^(8′)

43.0 43.1 —CH₃ —CH₃

29.0 29.1 —CH₃ —CH₃ 29.2 H H

36.0 36.1 H H

TABLE 3 Substituted 2,5-diaminoterephthalic acid dinitriles Substance R³ R² R⁴ R⁸ R⁶ R⁷

3.0

3.1

H H H H

3.2

—CH₃ H H —CH₃

3.3

H H H H

3.4

H H H H

3.5

H H H H

3.6

H H H H

3.7

H H H H

3.8

H H H H

3.9

H H H H

3.10

H H H H

3.11

H H H H

3.12

H H H H

3.13

H H H H

3.14

H H H H

3.15

H H H H

3.16

H H H H

3.17

—CH₃ H H —CH₃

3.18

H H H H

3.19

H H H H

3.20

H H H H

3.21

H H H H

3.22 —C₄H₉ H H H H —C₄H₉

3.23

H H H H

3.24

H H H H

3.25

H H H H

3.26

—CH₃ H H —CH₃

3.27

H H H H

3.28

—CH₃ H H —CH₃

3.29

—CH₃ H H —CH₃

3.30

—CH₃ H H —CH₃

3.31

H H

3.32

H H H H

3.33

—CH₃ H H —CH₃

3.34

H H H H

3.35

H H

3.36

H H

3.37

H H

3.38

H H

3.39

H H

3.40

H H H H

3.41

—CH₃ H H —CH₃

3.42

—CH₃ H H —CH₃

3.43

—CH₃ H H —CH₃

3.44

—CH₃ H H —CH₃

3.45

—CH₃ H H —CH₃

3.46

—CH₃ H H —CH₃

3.47

—CF₃ H H —CF₃

3.48

—CF₃ H H —CF₃

3.49

—CF₃ H H —CF₃

3.50

—CF₃ H H —CF₃

3.51

—CF₃ H H —CF₃

3.52

—CF₃ H H —CF₃

3.53

H H

3.54

H H

3.55

H H

3.56

H H

3.57

H H

3.58

H H

3.59

H H

3.60

H H

3.61

H H

3.62

—CH₃ H H —CH₃

3.63

H H

3.64

H H

3.65

H H

3.66

H H

3.67

H H H H

3.68

H H

3.69

—CH₃

—CH₃

3.70

3.71

Substance R² R³ R⁴ R⁶ R⁷ R⁸

48.0 48.1

H

H 48.2

H

H 48.3

H

H 48.4

H

H

44.0 44.1

H —CH₃

H 44.2

H

H 44.3

H Substance R⁸ R² R³ R⁶ R⁷ R⁴

46.0 46.1 H —CH₃

H 46.2 H

H Substance R⁴ R³ R² R⁸ R⁷ R⁶

49.0 49.1

45.0 45.1

H

47.0 47.1 H

TABLE 4 Substituted 2,5-diamino-3,6-dihydroterephthalic acid dinitriles Substance R³ R² R⁴ R^(4′) R⁸ R^(8′) R⁶ R⁷

4.0 —CH₃ —CH₃ —CH₃ —CH₃

4.1

H —CH₃ —CH₃ —CH₃ —CH₃ H

4.2

—CH₃ —CH₃ —CH₃ —CH₃ —CH₃ —CH₃

4.3

H —CH₃ —CH₃ —CH₃ —CH₃ H

Substance R³ R²

4.4

H

4.5

H

4.6

H

4.7

H

4.8

H

4.9

H

4.10

H

4.11

H

4.12

H

4.13

H

4.14

H

4.15

H

4.16

H

4.17

—CH₃

4.18

H

4.19

H

4.20

H

4.21

H

4.22 —C₄H₉ H

4.23

H

4.24

H

4.25

H

4.26

—CH₃

4.27

H

4.28

—CH₃

4.29

—CH₃

4.30

—CH₃

4.31

H

4.32

—CH₃

4.33

H

4.34

4.35

4.36

4.37

4.38

4.39

H 4.40

—CH₃ 4.41

—CH₃ 4.42

—CH₃ 4.43

—CH₃ 4.44

—CH₃ 4.45

—CH₃ 4.46

—CF₃ 4.47

—CF₃ 4.48

—CF₃ 4.49

—CF₃ 4.50

—CF₃ 4.51

—CF₃ 4.52

4.53

4.54

4.55

4.56

4.57

4.58

4.59

4.60

4.61

—CH₃ 4.62

4.63

4.64

4.65

4.66

H 4.67

4.68

—CH₃ 4.69

4.70

Substance R⁴ R⁸ R⁶

4.4 —CH₃ —CH₃ H

4.5 —CH₃ —CH₃ H

4.6 —CH₃ —CH₃ H

4.7 —CH₃ —CH₃ H

4.8 —CH₃ —CH₃ H

4.9 —CH₃ —CH₃ H

4.10 —CH₃ —CH₃ H

4.11 —CH₃ —CH₃ H

4.12 —CH₃ —CH₃ H

4.13 —CH₃ —CH₃ H

4.14 —CH₃ —CH₃ H

4.15 —CH₃ —CH₃ H

4.16 —CH₃ —CH₃ H

4.17 —CH₃ —CH₃ —CH₃

4.18 —CH₃ —CH₃ H

4.19 —CH₃ —CH₃ H

4.20 —CH₃ —CH₃ H

4.21 —CH₃ —CH₃ H

4.22 —CH₃ —CH₃ H

4.23 —CH₃ —CH₃ H

4.24 —CH₃ —CH₃ H

4.25 —CH₃ —CH₃ H

4.26 —CH₃ —CH₃ —CH₃

4.27 —CH₃ —CH₃ H

4.28 —CH₃ —CH₃ —CH₃

4.29 —CH₃ —CH₃ —CH₃

4.30 —CH₃ —CH₃ —CH₃

4.31 —CH₃ —CH₃

—CH₃ —CH₃ H

4.32 —CH₃ —CH₃ —CH₃

4.33 —CH₃ —CH₃ H

4.34 —CH₃ —CH₃

4.35 —CH₃ —CH₃

4.36 —CH₃ —CH₃

4.37 —CH₃ —CH₃

4.38 —CH₃ —CH₃

4.39 —CH₃ —CH₃ H 4.40 —CH₃ —CH₃ —CH₃ 4.41 —CH₃ —CH₃ —CH₃ 4.42 —CH₃ —CH₃ —CH₃ 4.43 —CH₃ —CH₃ —CH₃ 4.44 —CH₃ —CH₃ —CH₃ 4.45 —CH₃ —CH₃ —CH₃ 4.46 —CH₃ —CH₃ —CF₃ 4.47 —CH₃ —CH₃ —CF₃ 4.48 —CH₃ —CH₃ —CF₃ 4.49 —CH₃ —CH₃ —CF₃ 4.50 —CH₃ —CH₃ —CF₃ 4.51 —CH₃ —CH₃ —CF₃ 4.52 —CH₃ —CH₃

4.53 —CH₃ —CH₃

4.54 —CH₃ —CH₃

4.55 —CH₃ —CH₃

4.56 —CH₃ —CH₃

4.57 —CH₃ —CH₃

4.58 —CH₃ —CH₃

4.59 —CH₃ —CH₃

4.60 —CH₃ —CH₃

4.61 —CH₃ H —CH₃ 4.62 —CH₃ H

4.63 —CH₃ H

4.64 —CH₃ H

4.65 —CH₃ H

4.66 —CH₃ H H 4.67 —CH₃ H

4.68

—CH₃ 4.69

4.70

Substance R⁷ R^(4′) R^(8′)

4.4

—CH₃ —CH₃

4.5

—CH₃ —CH₃

4.6

—CH₃ —CH₃

4.7

—CH₃ —CH₃

4.8

—CH₃ —CH₃

4.9

—CH₃ —CH₃

4.10

—CH₃ —CH₃

4.11

—CH₃ —CH₃

4.12

—CH₃ —CH₃

4.13

—CH₃ —CH₃

4.14

—CH₃ —CH₃

4.15

—CH₃ —CH₃

4.16

—CH₃ —CH₃

4.17

—CH₃ —CH₃

4.18

—CH₃ —CH₃

4.19

—CH₃ —CH₃

4.20

—CH₃ —CH₃

4.21

—CH₃ —CH₃

4.22 —C₄H₉ —CH₃ —CH₃

4.23

—CH₃ —CH₃

4.24

—CH₃ —CH₃

4.25

—CH₃ —CH₃

4.26

—CH₃ —CH₃

4.27

—CH₃ —CH₃

4.28

—CH₃ —CH₃

4.29

—CH₃ —CH₃

4.30

—CH₃ —CH₃

4.31

—CH₃ —CH₃

—CH₃ —CH₃

4.32

—CH₃ —CH₃

4.33

—CH₃ —CH₃

4.34

—CH₃ —CH₃

4.35

—CH₃ —CH₃

4.36

—CH₃ —CH₃

4.37

—CH₃ —CH₃

4.38

—CH₃ —CH₃

4.39

—CH₃ —CH₃ 4.40

—CH₃ —CH₃ 4.41

—CH₃ —CH₃ 4.42

—CH₃ —CH₃ 4.43

—CH₃ —CH₃ 4.44

—CH₃ —CH₃ 4.45

—CH₃ —CH₃ 4.46

—CH₃ —CH₃ 4.47

—CH₃ —CH₃ 4.48

—CH₃ —CH₃ 4.49

—CH₃ —CH₃ 4.50

—CH₃ —CH₃ 4.51

—CH₃ —CH₃ 4.52

—CH₃ —CH₃ 4.53

—CH₃ —CH₃ 4.54

—CH₃ —CH₃ 4.55

—CH₃ —CH₃ 4.56

—CH₃ —CH₃ 4.57

—CH₃ —CH₃ 4.58

—CH₃ —CH₃ 4.59

—CH₃ —CH₃ 4.60

—CH₃ —CH₃ 4.61

—CH₃ —CH₃ 4.62

—CH₃ —CH₃ 4.63

—CH₃ —CH₃ 4.64

—CH₃ —CH₃ 4.65

—CH₃ —CH₃ 4.66

—CH₃ —CH₃ 4.67

—CH₃ —CH₃ 4.68

—CH₃ —CH₃ 4.69

—CH₃ —CH₃ 4.70

—CH₃ —CH₃ Substance R² R³ R⁴ R⁶ R⁷ R⁸ R^(8′) R^(4′)

56.0 56.1

—CH₃

—CH₃ —CH₃ —CH₃ 56.2

—CH₃

—CH₃ —CH₃ —CH₃ 56.3

—CH₃

—CH₃ —CH₃ —CH₃ 56.4

—CH₃

—CH₃ —CH₃ —CH₃ Substance R² R³ R⁶ R⁷ R⁸ R^(8′) R⁴ R^(4′)

50.0 50.1

—CH₃

—CH₃ —CH₃ —CH₃ —CH₃ 50.2

—CH₃ —CH₃ —CH₃ —CH₃ 50.3

—CH₃

—CH₃ Substance R⁸ R^(8′) R³ R⁶ R⁷ R⁴ R^(4′) R²

53.0 53.1 —CH₃ —CH₃

—CH₃ —CH₃ —CH₃ 53.2 —CH₃ —CH₃

—CH₃ —CH₃

Substance R^(4′) R³ R² R^(8′) R⁷ R⁶ R⁴ R⁸

57.0 57.1

—CH₃ —CH₃

51.0 51.1

H

—CH₃ —CH₃ Substance R⁴ R^(4′) R³ R² R⁶ R⁷ R^(8′) R⁸

54.0 54.1 —CH₃ —CH₃

—CH₃ Substance R⁴ R^(4′) R³ R² R⁶ R⁷ R^(8′) R^(8′)

52.0

52.1

—CH₃ —CH₃

55.0

55.1 —CH₃ —CH₃

58.0

58.1

The new emitters are used in a device comprising or not comprising an electron transport layer, wherein the layers in a device can be arranged as shown in FIG. 2:

-   1. The substrate consists of a transparent material, e.g. glass; -   2. The anode consists of ITO which injects the holes into the hole     transport layer; -   3./4. The hole conductor mainly consists of triphenylamine     derivatives; several hole conductor layers can be provided whose     characteristics are adapted to the device; -   5. Between the hole conductor and the electron conductor, one or     more emitter layers are arranged; -   6. The electron conductor can e.g. consist of Alq3 and conducts the     electrons from the cathode to the emitting layer or the hole     conductor inside the device; -   7. The buffer layer consists of certain metal salts or the oxides     thereof, e.g. LiF, and improves the electron injection into the     layer 6; -   8. The cathode consists of a base metal or an alloy (e.g. aluminium     or calcium).

Typically, the emitter layers are 3–10 nm thick, preferably 4–6 nm. The emission wavelengths depend on the chemical structure in a characteristic manner, i.e. electronic and steric factors of the molecules obviously influence the wavelength of the emitted light and the performance achieved. The wavelengths of the examples listed in Table 2 range between 538 nm and 618 nm.

In order to achieve mixed colours, the new emitters of formulas 1.0–58.0 can be arranged on top of one another, either in the form of several layers each of which consists of an emitter material in its pure form (FIG. 2) or in the form of one or several layer(s) in which the emitter materials are provided in a mixed form.

The layers comprising the new emitters of formulas 1.0–58.0 can be doped with known emitter materials, as shown in FIG. 1.

The new emitters of formulas 1.0–58.0 can be used in devices comprising hole conductors known per se (59 and 60) and other components. Typical examples are shown in FIGS. 1 and 2.

4,4′,4″-tris(N-(α-naphthyl)-N-phenylamino)-triphenylamine (1-NAPHDATA)

N,N′-di(α-naphthyl)-N,N′-diphenylbenzidine (α-NPD)

The devices based on the new emitters can be produced in a manner known per se, i.e. by vacuum deposition at between 1 and 10⁻⁹ torrs.

Alternatively, the devices can be produced by solution coating, e.g. web coating or spin coating. Here, the new emitters of formulas 1.0–58.0 can be applied either as the pure substance or as a dopant contained in a suitable polymer.

Surprisingly, it has been found that particularly efficient devices can be produced using substances of the formula 1.0 which have been substituted with fluorine. A remarkably high photometric efficiency is observed in these cases. Using the substance 1.2, a device emitting a spectrally nearly pure green is obtained.

EXPERIMENTAL PART

The following examples are intended to illustrate the invention in more detail, but do by no means limit the same.

Example 1 (Substances 2.1, 2.3–2.5)

0.06 mol cyclohexane-2,5-dione-1,4-dicarboxylic acid diester is suspended in a mixture of 200 ml glacial acetic acid and 200 ml alcohol (corresponding to the ester component). In a nitrogen atmosphere, 0.135 mol of a primary amine or aniline is speedily added. The reaction mixture is refluxed for 5–8 hours while stirring thoroughly. Anilines which have been substituted with an acceptor require longer reaction times.

In the case of anilines, the crude product can be isolated by sucking off the cooled-down reaction mixture, thoroughly washing it with methanol and drying.

Aliphatic amines form highly soluble products, i.e. the solvent must be separated almost completely using a rotary evaporator. The crude product is added into methanol, thoroughly cooled, sucked off and dried.

Example 2 (Substances 1.1, 1.31.5)

The esters of dihydroterephthalic acid obtained in Example 1 are oxidized. Yields of up to 95% are achieved during isolation. In order to purify the separated crude product, it can be recrystallized from DMF, toluene, chloroform or methanol. The substances obtained are sublimable.

Example 3 (Substances 19.1–19.4)

The esters obtained according to Example 2 are saponified in mixtures of n-propanol and water. 0.01 mol terephthalic acid diester is suspended in approx. 50 ml n-propanol, and 50 ml water containing 0.03 mol potassium hydroxide is added. The suspension is refluxed until a clear solution is obtained. Once another 2 hours have passed, the liquid is sucked off. In order to neutralize the solution, approx. 5 ml glacial acetic acid is added dropwise. The acid obtained is washed with methanol and dried.

In order to produce the substances 19.1–19.4, 0.01 mol of the terephthalic acid obtained is refluxed for 2 hours in 100 ml glacial acetic acid to which 15 ml formaldehyde solution (37%) has been added.

The reaction products are separated and washed with methanol. They are recrystallized from acetonitrile or chloroform. The substances obtained can be purified by sublimation.

Example 4 (Substance 1.2)

In order to obtain compounds of this type, the respective terephthalic acid ester (Example 2) can be alkylated. 0.05 mol terephthalic acid ester is suspended in 350 ml anhydrous DMSO, and 18.63 g (0.131 mol) methyl iodide is added. 6.1 g (0.152 mol) 60% sodium hydride in paraffin is added in portions at a temperature ranging between 20 and 23° C. and while stirring throrougly. Once a reaction time of approx. 5 hours has passed, the colour of the solid constitutents has changed from orange to pure yellow. Now, approx. 200 ml methanol is added to the mixture, thereby considerably improving filterability.

The separated yellow reaction product is thoroughly washed with methanol and dried. A pure product is obtained by recrystallization from toluene.

Example 5 (Device: Substance 19.4)

A 55 nm thick layer of 4,4′,4″-tris(N-(α-naphthyl)-N-phenylamino)-triphenylamine and another 5 nm thick layer of N,N′-di(α-naphthyl)-N,N′-diphenylbenzidine were deposited onto a structured ITO glass substrate measuring 50×50 mm². Onto these hole transport layers, 5 nm 1,6-bis(2,4-dimethoxyphenyl)-benzo[1,2-d;4,5-d′]-1,2,6,7-tetrahydro-bis[1,3]oxazine-4,9-dione (19.4) is deposited.

In addition, a 30 nm thick layer of tris-(8-hydroxychinolinato)-aluminium is now applied onto this emitter layer, followed by a very thin buffer layer (0.5 nm) of lithium fluoride and finally aluminium.

The arrangement was tested applying an adjustable voltage between 0 and 15 V. The device emits a wavelength of 578 nm (yellow). A luminance (emission intensity) of 100 cd/m² was achieved at 5.0 V. The maximum luminance (emission intensity) achieved was 11,400 cd/m².

Example 6 (Device: Substance 1.21)

A device was produced according to Example 5, into which a 5 nm thick layer of 2,5-bis-(N-(2,4-dimethoxyphenyl)amino)terephthalic acid diethyl ester was incorporated as emitter substance between the hole conductor and the electron conductor.

The device was also tested applying an adjustable voltage between 0 and 15 V. The device emits a wavelength of 618 nm (red). A luminance (emission intensity) of 100 cd/m² was achieved at 9.5 V. The maximum luminance (emission intensity) achieved was 644 cd/m².

Example 7 (Device: Substance 1.5)

The device has the same structure as those of Examples 5 and 6. The emitter substance used was 2,5-bis-(N-phenylamino)-terephthalic acid diethyl ester.

Once again, the device was tested applying an adjustable voltage between 0 and 15 V. The device emits a yellow light (578 mm). A luminance (emission intensity) of 100 cd/m² was achieved at 5.6 V. The maximum luminance (emission intensity) recorded was 5,300 cd/m².

Example 8 (Device: Substance 1.2)

Analogously to Examples 5–7 and according to the same structural principle, a 5 nm thick layer of N,N′-dimethyl-2,5-bis-(N-(2-fluorophenyl)-amino)terephthalic acid dimethyl ester was deposited onto the hole transport layers.

The arrangement (FIG. 2) was tested applying an adjustable voltage between 0 and 15 V. The device emits a green light (λ_(max)=547 nm). A luminance (emission intensity) of 100 cd/m² was achieved at 5.4 V. The maximum luminance (emission intensity) achieved was 17,700 cd/m².

-   1. The substrate consists of glass; -   2. The anode consists of ITO; -   3. 1-Naphdata is applied as hole conductor; -   4. Another hole conductor layer consists of α-NPD; -   5. One or several emitter layers are arranged between the hole     conductor and the electron conductor; -   6. The electron conductor can e.g. consist of Alq3; -   7. The buffer layer consists of LiF; -   8. The cathode consists of a base metal or an alloy (e.g. aluminium     or calcium).

Typically, the emitter layers are 3–10 nm thick, preferably 4–6 nm.

Photometric Parameters of Selected Emitter Substances

TABLE 2 # ¹⁾V ²⁾nm Colour ³⁾cd/m² ⁴⁾cd/A ⁵⁾lm/W  1.21 9.2 629 red-white 1980 0.12 0.07  1.16*⁾ 9.3 634 red-white 3990 0.14 0.10  1.16 14.0 618 red 144 0.09 0.07  1.30 5.6 612 orange-red 12100 2.17 2.27 19.4 5.0 578 yellow 11400 2.04 1.72  1.5 5.6 578 yellow 5300 1.59 1.42  1.4 8.0 577 yellow 1410 0.81 0.37 19.3 6.5 565 yellow-green 4530 0.72 0.49  1.3 8.1 577 yellow-green 4330 2.77 1.52 19.7 10.2 yellow-green 474 0.26 0.10  1.34 3.5 550 green 36500 1.00 9.21  1.36 5.7 546 green 18100 6.60 4.34  1.2 5.4 547 green 17700 7.70 4.93  1.38 6.4 546 green 11300 4.62 2.47 19.2 6.6 564 green 6010 0.89 0.66 19.1 6.7 540 green 4680 3.05 1.70 19.6 8.6 545 green 2610 0.52 0.36  1.29 11.1 564 green 1330 1.59 0.47  1.1 7.1 538 green 1300 0.48 0.22  1.33 10.3 563 green 1100 1.53 0.54  1.31 10.8 566 green 754 1.60 0.53 19.8 13.4 green 273 1.20 0.70 19.11 14.4 532 green 144 0.03 0.01 19.5 >20.0 540 green 8 0.30 0.28 19.9 >15.0 544 green 64 0.58 0.13 ¹⁾voltage at 100 cd/m² ²⁾λ_(max) of electroluminescence ³⁾max. luminance (emission intensity) ⁴⁾max. photometric efficiency ⁵⁾max. performance efficiency

TABLE 3 Table 3# λ_(max) (solid) λ_(em) (solid) 1.6 614 1.7 597 1.8 604 1.10 626 1.11 596 1.12 586 1.1 547 1.13 559 1.14 543 1.15 605 1.16 500 635 1.17 596 1.18 617 1.19 435 531 1.4 599 1.20 596 19.1 475 564 19.4 460 598 1.5 465 582 1.21 495 625 19.5 612 1.23 573 1.24 564 1.25 605 1.26 602 19.3 582 1.6 623 19.6 592 1.28 588 1.3 595 1.24 612 19.8 453 583 1.2 558 1.5 496 622 λ_(max): absorption maximum λ_(em): emission maximum λ_(ell): maximum of electroluminescence

TABLE 4 Absorbance coefficients ε of selected emitter substances # λ_(max) (nm) ε (l · mol⁻¹ cm⁻¹) Solvent 1.16 489 6000 CHCl₃ 1.5 469 6640 CHCl₃ 1.34 403 4744 NMP 19.6 452 5250 CHCl₃ 19.5 474 4670 CHCl₃ 19.7 433 5450 NMP 1.17 472 6410 CHCl₃ 1.15 486 5930 CHCl₃ 1.12 460 5930 CHCl₃ 1.11 481 6840 CHCl₃ 1.8 472 6450 CHCl₃ 1.7 474 6550 CHCl₃ 19.1 434 4700 NMP 1.30 493 5450 NMP 1.27 482 6800 CHCl₃

TABLE 5 Absorption maxima of selected emitter substances in solution# λ_(max) (NMP) 1.6 482 1.7 476 1.8 463 1.9 652 1.10 509 1.11 475 1.12 445 1.1 413 1.13 427 1.14 428 1.15 482 1.16 494 1.17 464 1.18 464 1.19 417 1.4 468 1.20 461 19.1 435 19.4 458 1.5 451 1.21 479 1.22 505 19.5 472 1.23 432 1.24 446 1.25 487 1.26 482 19.3 447 1.6 481 19.6 452 1.28 473 1.3 451 1.24 480 1.30 493 1.34 403 1.5 461 1.43 496

TABLE 6 DSC values of selected emitter substances# DSC peak in ° C. 19.3 260.0 1.6 269.1 1.7 171.3 1.8 227.8 1.11 192.1 1.12 172.2 1.15 232.0 1.17 166.5 19.1 325.7 1.16 183.3 1.34 254.7 19.1 325.7 1.27 182.5

Preparation and Measuring Conditions

a) Substrate: 125 nm ITO, approx. 13 Ω/sq and 85% tranmission, 50×50 mm² glass substrate (1.1 mm thick polished soda-lime float glass with SiO₂ layer and 8 individual ITO anodes (active surface area: 2×2 mm²))

Purified 2×20 min in an ultrasonic bath with Aceton selectopur and Methanol selectopur,

-   3× snow jet cleaning (CO₂ ice crystals) -   O₂ plasma treatment (5 min at 450 W and 0.12 mbar)

b) Pressure (2–4)×10⁻⁵ mbar during deposition

-   Aluminium oxide ceramic crucible -   Deposition rate: 0.06 nm/s -   Layer thickness checked using a piezoelectric microbalance measuring     device

Change of mask and intermediate aeration of the deposition chamber, first with nitrogen and then with air

-   Cathodes, 0.5 nm lithium fluoride (insulating) and 100 nm aluminium     each

c) The device according to FIG. 2 was introduced in a glove box, the active OLED suface was positioned above calibrated V_(λ) silicon photodiodes in a darkened measuring device, and the anode (ITO-) and cathode (A1-) contacts were brought in contact with gilded spring electrodes

Programmable voltage supply (SMU) and digital multimeter for recording and processing the OLED curve in a PC via GPIB-BUS and LabView program

Voltage pulse operation (pulses lasting 1 s) between −10 V and +15 V (0.5 V increments): current density-voltage curve and luminance (emission intensity)-voltage curve as well as the calculated photometric efficiency values (in cd/A) and performance efficiency values (in 1 m/W) as a function of U

d) Wavelength of maximum by recording the electroluminescence spectrum using an Xdap diode array spectrometer 

1. A 2,5-diaminoterephthalic acid derivative of formula 19,

wherein X¹ and X³ are O, X² and X⁴, which can be the same or different, are O or N; R² and R⁶ are methylene (—CH₂—), which can be substituted with trifluoromethyl, R³ and R⁷ are the same or different, H, C₁–C₈ alkyl, aryl, or heteroaryl, and R⁴ and R⁸ are the same or different, H, alkyl, aryl or trifluoromethyl, and R¹ and R⁵, which can be the same or different and are H, C₁–C₄ alkyl or phenyl with the proviso that R¹ is absent if X² is O and R⁵ is absent if X⁴ is O.
 2. The derivative of claim 1, wherein alkyl is C₁–C₄ alkyl, aryl is phenyl or naphthyl, and heteroaryl is pyridyl, thienyl or furyl.
 3. The derivative of claim 1, wherein alkyl is C₁–C₈ alkyl, aryl is phenyl or naphthyl, and heteroaryl is cumaryl, pyridyl, chinolyl, indolyl, carbazolyl, imidazolyl, thienyl, thiazolyl, furyl or oxazolyl.
 4. The derivative of claim 1, wherein R⁴ and R⁸ are trifluoromethyl, 2-fluorophenyl, 3-fluorophenyl, 4-flurophenyl, 2,4,-difluorophenyl, 2,6-difluorophenyl, 2,3,4,5-tetrafluorophenyl or pentafluorophenyl.
 5. The derivitive of claim 1, wherein R⁴ and R⁸ are the same or different and are hydrogen, C₁–C₈ alkyl or phenyl.
 6. The derivative of claim 1, wherein R⁴ and R⁸ are the same or different and are hydrogen, C₁–C₄ alkyl or phenyl.
 7. The derivative of claim 6, wherein R¹ and R^(8 are H.)
 8. The derivative of claim 1, wherein R¹ and R⁵ are C₁–C₄ alkyl or phenyl, and X² and X⁴ are nitrogen.
 9. The derivative of claim 1, wherein X² is N.
 10. The derivative of claim 1, wherein X² is O.
 11. The derivative of claim 1, wherein R³ and R⁷ are 2-fluorophenyl, 3-fluorophenyl, 4-flurophenyl, 2,4,-difluorophenyl, 2,6-difluorophenyl, 2,3,4,5-tetrafluorophenyl or pentafluorophenyl.
 12. The derivative of claim 1, wherein R³ and R⁷ are the same or different and are substituted or unsubstituted phenyl, said substituted phenyl being substituted singly or multiply with halogen, CN, C₁–C₄ alkyl, C₁–C₄ alkoxy, amino or phenyl.
 13. The derivative of claim 12, wherein R³ and R⁷ are N,N-dimethyl-4-aminophenyl, and R⁴ and R⁸ are H.
 14. The derivative of claim 12, wherein X² and X⁴ are O, R³ and R⁷ are 4-cyanophenyl, and R⁴ and R⁸ are H.
 15. The derivative of claim 1, wherein R³ and R⁷ are the same or different and are substituted or unsubstituted phenyl, said substituted phenyl being substituted singly or multiply with fluoro, chloro, CN, methyl, methoxy, trifluoromethyl, or phenyl.
 16. The derivative of claim 1, wherein X² and X⁴ are O, R³ and R⁷ are phenyl, and R⁴ and R⁸ are H.
 17. The derivative of claim 1, wherein X² and X⁴ are O, and R⁴ and R⁸ are H.
 18. The derivative of claim 17, wherein R³ and R⁷ are substituted or unsubstituted α-naphthyl.
 19. The derivative of claim 17, wherein R³ and R⁷ are substituted or unsubstituted β-naphthyl.
 20. The derivative of claim 17, wherein R³ and R⁷ are substituted or unsubstituted phenyl.
 21. The derivative of claim 20, wherein R³ and R⁷ are the same or different and are substituted phenyl, said phenyl substituted singly or multiply with C₁–C₄ alkyl, C₁–C₄ alkoxy or a combination thereof.
 22. The derivative of claim 21, wherein R³ and R⁷ are 2,4-dimethylphenyl.
 23. The derivative of claim 1, wherein X² and X⁴ are N.
 24. The derivative of claim 23, wherein R¹ and R⁵ are phenyl.
 25. The derivative of claim 23, wherein R¹ and R⁵ are C₁–C ₄ alkyl.
 26. The derivative of claim 23, wherein R³ and R⁷ are substituted or unsubstituted α-naphthyl.
 27. The derivative of claim 23, wherein R³ and R⁷ are substituted or unsubstituted β-naphthyl.
 28. The derivative of claim 23, wherein R³ and R⁷ are substituted or unsubstituted phenyl.
 29. The derivative of claim 28, wherein R³ and R⁷ are the same or different and are substituted phenyl, said phenyl substituted singly or multiply with C₁–C₄ alkyl, C₁–C₄ alkoxy or a combination thereof.
 30. The derivative of claim 28, wherein R³ and R⁷ are 2,4-dimethylphenyl.
 31. The derivative of claim 28, wherein R³ and R⁷ are the same or different and are substituted phenyl, said phenyl substituted singly or multiply with halogen, nitro, cyano, amino, C₁–C₈ alkyl or phenyl.
 32. The derivative of claim 28, wherein R³ and R⁷ are the same or different and are substituted phenyl, said phenyl substituted singly or multiply with halogen, C₁–C₄ alkyl, trifluoromethyl, C₁–C₄ alkoxy or a combination thereof.
 33. The derivative of claim 1, wherein R³ and R⁷ are the same or different and are C₁–C₄ alkyl, unsubstituted phenyl, or substituted phenyl. 